Process for the dyeing of polymers of acrylonitrile or asymmetric dicyanoethylene



United States Patent 0 PROCESS FOR THE DYEING 0F POLYMERS 0FACRYLONITRILE 0R AsYMMETRIc DICYANO- ETHYLENE Heinz Werner Schwechten,Josef Singer, and Otto Bayer,

Leverkusen-Bayerwerk, Germany, assignors to Far-benfabriken BayerAktiengesellschaft, Leverkusen, many, a corporation of Germany NoDrawing. Application May 22, 1956 Serial No. 586,388

Claims priority, application Germany May 28, 1955 12 Claims. (Cl. 839)This invention relates to the dyeing of polymers based on acrylonitrileor asymmetrical dicyanoethylene with basic anthraquinone dyestuffs.

We have found that basic arylamino-anthraquinones which are substitutedin the aryl group by radicals containing one or more aliphaticallylinked amino groups which may be substituted or quaternized, and whichcan be substituted in the anthraquinone radical by other groups, arevery suitable for the dyeing of polymers or Ger- ' or'quaternized, forexample, by alkylor cycloalkyl groups 5 chain or via an 2,900,216 aented Aus- 1 1.95.

co-polymers based on acrylonitrile or asymmetrical dicyanoethylene.

whereby the alkyl groups may j also'j'form a heterocyclic ring, forexample CHLVCH:

N/ 0.3: I s OKs-Cg:

The aryl radical and the anthraquinone radical may themselves besubstituted, for example, by halogenor a hydroxyl-, alk0xy-, amindor'substituted amino group.

7 Examples of'siich dyestufis are:

Shade on polyecrylonitrile (staple fiber type Orlon 42 (Du Pont))NEE-0H3 ii Nn--em.mcm

(a) r YNH,

1 reddish blue.

CH;.N(OH3):

greenish blue.

clear blue.

Hi-QE:

CH: CHI-C Shade on polyacrylonitrile (staple fiber type Orlon 42 (DuPont (6) (f 11TH; clear blue.

m CH1. CH1 g NH O.CH;.CH:.N\ Q 7 CHgIJg (7) (I) NH: Do.

I 0 NH-S.CH:.CH:.N(CH:):

(8) h) N H, blue.

I CH3-C o-NH o NH CHs.N(CHa)2 (9) OH violet.

m Hz-NwHah reddish blue.

P N H C H:.N (C H 2 l O H (11) 0H,.NH, green.

f) NH CH C H .NH,

I11 H 0 H3 0 NH: blue.

C H:N

G H; NH

( 3) (I) I?! H C H; greenish blue.

C Ha-N Shade on polyacrylonitrile (staple fiber type Orlon 42 (Du Pont))(14) (I) NH-C IHOH (15) O NH;

blue.

greenish blue.

The anthraquinones used for the new process may be obtained in knownmanner, for example, by reacting halogen-anthraquinones with amines ofthe general formula The dyestuffs thus obtained can be quaternized by,

known methods.

The dyeing of the polymers of acrylonitrile or asymmetricdicyanoethylene is effected from a slightly acid bath at elevatedtemperature, if desired in a closed vessel at temperatures above 100 C.in known manner. full shades thus obtained distinguish themselves bytheir very good fastness to wetting and some of them by very goodfastness to light. Co-polymers of acrylonitrile or asymmetricdicyanoethylene which contain for example acrylic acid esters or vinylacetate can be used also for theprocess of the present invention; 7 Thedyestuffs are also very well suited for spinning into polymers based onacrylonitrile according to the well known dry spinning process from adimethylformamide solution.

The present invention is further illustratedby the following examples,without, in any way; limiting it there- Example 1 Hanks of co-polymersof acrylonitrile are dyed on the boiling water bath for an hour in anaqueous solution The p containing 1 percent (referred to the weight ofthe dyeing goods) of a dyestufi of the following general formula:

using a liquor-to-goods ratio of 40:1, with the addition of 3 percent of30 percent acetic acid and 1.5 grams of sodium acetate. A full reddishblue dyeing is obtained of very good fastness to wetting and to light.

Example 2 Hanks of co-polymers of asymmetric dicyanoethylene are dyedaccording to the instructions given in Example 1, with 1 percent of adyestufr' of the general formula:

A full and pure blue dyeing is obtained having good fastness to wettingand very good fastness to light.

Example 3 blue dyeing is obtained of very good fastness to wetting andto light.

in which R is a member selected from the group consisting of a loweralkylene radical, an oxy-lower alkylene radical, a thio-lower alkyleneradical and an imino-lower alkylene radical, and Y is a member selectedfrom the group consisting of an unsubstituted, lower-alkyl-substitutedand quaternized amino group.

2. A process as in claim 1 wherein R is a lower alkylene radical, Y isan unsubstituted amino group and the phenyl nucleus is furthersubstituted by a lower alkyl radical.

3. A process as in claim 1 wherein R is a lower alkylene radical, Y is adi-lower alkyl substituted amino group and the phenyl nucleus is furthersubstituted by a lower alkyl radical.

4. A process as in claim 1 wherein R is an N-lower alkyl imino loweralkylene radical and Y is a di-lower alkyl substituted amino group.

5. A process for the dyeing of a polymer based on a member selected fromthe group consisting of acrylonitrile, asymmetrical dicyanoethylene andcopolymers thereof in an acid dye bath which comprises using as dyestufia compound of the formula l o NHGC Hz.N(CHa)2 6. A process for thedyeing of a polymer based on a member selected from the group consistingof acrylonitrile, asymmetrical dicyanoethylene and copolymers thereof inan acid dye bath which comprises using as dyestuff a compound of theformula f NH:

I l o zen-@oczmcmMmm):

7. A process for the dyeing of a polymer based on a member selected fromthe group consisting of acrylonitrile, asymmetrical dicyanoethylene andcopolymers thereof in an acid dye bath which comprises using as dyestuffa compound of the formula I O NH 8. A process for the dyeing of apolymer basedon a member selected from the group consisting ofacrylonitrile, asymmetrical dicyanoethylene and copolymers thereof in anacid dye bath which comprises using as dyestufi a compound of theformula CH .NH3

O N H CH 5 l g I CH:.NH: 1 0 O N H U H3 9. A member selected from thegroup consisting of a polymer based on acrylonitrile, asymmetricaldicyanoethylene and co-polymers thereof which has been dyed with acompound of the formula f N H:

ii NHQCHLNUJHQI 10. A member selected from the group consisting of apolymer based on acrylonitrile, asymmetrical dicyanoethylene andco-polymers thereof which has been dyed with a compound of the formula I0 NHQ-OH;

12. A member selected from the group consisting of a polymer based onacrylonitrile, asymmetrical dicyanoethylene and co-polymers thereofwhich has been dyed with a compound of the formula Vickerstafi: ThePhysical Chem. of Dyeing, 2nd ed., 1954, Intersci. Publ. Inc., p. 17.

1. A PROCESS FOR THE DYEING OF A POLYMER BASED ON A MEMBER SELECTED FROMTHE GROUP CONSISTING OF ACRYLONITRILE, ASYMMETRICAL DICYANOETHYLENE ANDCOPOLYMERS THEREOF IN AN ACID DYE BATH WHICH COMPRISES USING AS DYESUFFSTUFF A BASIC PHENYLAMINOANTHRAQUINONE WHICH IS SUBSTITUTED IN THEPHENYL NUCLEUS BY A RADICAL HAVING THE FORMULA